Evaluation of the application of nanofiltration to concentrate the hydroethanolic extract obtained from grape juice marc N. B. EITEL, A. P. G. CRUZ, L. F. M. DA SILVA, S. P. FREITAS, L. M. C. CABRAL NATALIA BARBOSA EITEL natalia.eitel@poli.ufrj.br

Outline Introduction Materials & Methods Results Final Remarks Acknowledments References

Introduction Brazilians Grape Production Destinations (2000-2011) (Adapted from Mello (2005), Mello (2008), Mello (2012)) What should we do with the grape marc???

Introduction Alternative grape marc applications: Biochemical process feed stock (Bustamante et al., 2008) Enzyme Production Yeast Production Raw Material for the cosmetic industry (Brazinha et al., 2010 ) In Brazil, it’s still used as agricultural inputs: Animal feed Fertilizer

Introduction Bioactive Compounds = Thermolabile High cost of treatment Large recovery potential Rich phenolic composition Great antioxidant potential Biodegradation resistance ↓pH ↑ Phytotoxic compounds Solution! Membrane Separation Process: Nanofiltration!

Introduction Energy savings; Selectivity; Separation of thermolabile compounds; Simplicity of operation. The use of solvents can hinder a membrane separation processes Nanofiltration Habert et al. (2006) Tsui & Cheryan (2004)

Main Aims To recover the phenolic compounds present in the grape marc, particularly flavonoids from the seeds and peels To concentrate them

Acidified with citric acid Materials & Methods Grape Marc: 2010/2011 harvest courtesy of Aurora winery (RS/Brazil) Hydroethanolic Extraction: Extraction in semi-pilot scale with: EtOH = 30% pH = 4,0 Solvent: Substrate Ratio = 9 Acidified with citric acid

Materials & Methods Hydration without stirring at T = 30 ° C Extraction at 50 ° C for 120 minutes at 48RPM Centrifugation Choice of the best NF conditions through limiting flux definition Nanofiltration of the hydroethanolic extract .

Materials & Methods Limiting flux at different temperatures at a flow rate of 700 L h-1 Limiting flux reached at 20°C and 30°C with pressure of 16 bar and at 40°C with a transmembrane pressure of 12 bar

Materials & Methods => NANOFILTRATION: Spiral wound polyamide membrane modules system with filter area of 2,5m2; 40°C; ΔP = 12 bar; Javerage= 14,9 kg∙h‑1∙m-2; Fed Batch until . VCF= V(Retantate) V(Permeate) ≥10 Main aims: Concentrate the extract in bioactive compounds - RETENTATE Recover the extraction solution - PERMEATE

Materials & Methods Quantification of bioactive compounds: Total Phenolics (TP) – Singleton & Rossi (1965) modified by Georgé et. al. (2005) Total and Monomeric Anthocyanins (TA/MA) – Giusti & Wrolstad (2001) Antioxidant Activity (AA) – Rufino et. al. (2007) and RE et. al. (1999)

Results

Results J0 = 23,8 kg.h‑1.m-2 Javerage= 14,9 kg·h‑1·m-2

Analytical Results Obtained For The Different Process Streams Analysis AA (μmol∙g-1 extract) TP (mg∙100g-1 extract) TA (mg∙100g-1 extract) MA (mg∙100g-1 extract) Feed 4,32 ± 0,13 55,40 ± 2,77 13,71 ± 0,07 10,90 ± 0,06 Retentate 49,02± 6,72 593,17 ± 25,64 155,23 ± 3,48 119,42 ± 4,13 Permeate N/D VCF 10,14 R 100% N/D- Not Detected VCF= V(Retantate) V(Feed) and R= 1− c Permeate c Feed ×100%

Results Feed Retentate Permeate

Final Remarks NF = attractive alternative for the concentration of bioactive compounds recovered from the grape marc through a hydroethanolic extraction: 40°C; ΔP = 12 bar; J average= 14,9 kg∙h‑1∙m-2 Other tests should be performed in larger scale to confirm these results Suggestion: to determine the influence of other process parameters on its concentration and its permeate flux.

Acknowledgments

References C. Brazinha et al. (2010), Filtration+Separation, 47, pp. 32-35. P. Bridle et al. (1997), Food Chemistry, 58, pp. 103-109. M. A Bustamante et al. (2008), Waste Management, 28, 372–380. S. Georgé et al. (2005), J. of Agricultural and Food Chemistry, 53, 1370-1373. M. M. Giusti et al. (2001), Characterization and measurement of anthocyanins by UV-visible spectroscopy, In: Current Protocols in Food Analytical Chemistry, New York: Wiley. A. C. Habert et al. (2006), In: Processos de Separação por Membranas, Rio de Janeiro, E-papers. L. R. Mello (2005). Produção e Comercialização de Uvas e Vinhos – Panorama 2004. Bento Gonçalves, RS: EMBRAPA Uva e Vinho. L. R. Mello (2008). Vitivinicultura brasileira: panorama 2007. Bento Gonçalves, RS: EMBRAPA Uva e Vinho. L. R. Mello (2012). Vitivinicultura brasileira: Panorama 2011. Bento Gonçalves, RS: EMBRAPA Uva e Vinho. R. Re et al. (1999), Free Radic. Biol. Med., 26, 1231-1237. M. S. Rufino et al. (2007), Metodologia Científica: Determinação da atividade antioxidante total em frutas pela captura do radical ABTS+, Comunicado Técnico Embrapa Agroindústria Tropical, 128. V. L. Singleton et al. (1965), Am. J. Enol. Vitic., 16, 144-168. E. M. Tsui et al. (2004), J. of Membrane Science, 237, 61–69

Natalia Barbosa Eitel natalia.eitel@poli.ufrj.br Thank you! Natalia Barbosa Eitel natalia.eitel@poli.ufrj.br